+

WO1999031178A1 - Compositions elastomeres transparentes et colorables - Google Patents

Compositions elastomeres transparentes et colorables Download PDF

Info

Publication number
WO1999031178A1
WO1999031178A1 PCT/US1998/026716 US9826716W WO9931178A1 WO 1999031178 A1 WO1999031178 A1 WO 1999031178A1 US 9826716 W US9826716 W US 9826716W WO 9931178 A1 WO9931178 A1 WO 9931178A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
rubber
para
silica
parts
Prior art date
Application number
PCT/US1998/026716
Other languages
English (en)
Inventor
Walter H. Waddell
Robert R. Poulter
Kenneth Mcelrath
John Rogers
Original Assignee
Exxon Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Priority to JP2000539089A priority Critical patent/JP2002508425A/ja
Priority to DE69817398T priority patent/DE69817398T2/de
Priority to AT98963235T priority patent/ATE247691T1/de
Priority to EP98963235A priority patent/EP1040163B1/fr
Priority to BR9814192-9A priority patent/BR9814192A/pt
Priority to CA002306270A priority patent/CA2306270A1/fr
Priority to KR1020007005237A priority patent/KR20010032104A/ko
Publication of WO1999031178A1 publication Critical patent/WO1999031178A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C08L23/283—Iso-olefin halogenated homopolymers or copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

  • the present invention relates to transparent and colorable elastomeric compositions and, more particularly, to transparent and colorable elastomeric compositions that can be used in reinforcing applications.
  • Rubber compositions are used in a variety of applications, including tire components such as treads and sidewalls, hoses, belts, solid tires, rollers for graphic arts applications, footwear components, vibration isolation devices and bladders. While the particular rubber compositions used in each of these applications vary widely in their physical properties, one attribute remains the same - their color. Most aibber compositions are black. Furthermore, most rubber compositions eventually become discolored due to heat, light, ozone, etc. This is particularly true for rubbers used in stressful, demanding applications such as tire treads, sidewalls, bladders, belts and hoses.
  • White sidewalls on tires are a form of colorable rubber.
  • the white color is achieved by using fillers such as silica, clay, talc and carbonates instead of carbon black and adding titanium dioxide as a whitening pigment.
  • fillers such as silica, clay, talc and carbonates instead of carbon black and adding titanium dioxide as a whitening pigment.
  • the fillers are more fragile than carbon black and result in a weak rubber composition that does not reinforce the tire. Therefore, the rubbers used for white sidewalls are also limited in their usefulness.
  • the present invention provides improved transparent and colorable elastomeric compositions.
  • the transparent elastomeric compositions can be covulcanized with rubbers such as polybutadiene, polyisoprene, styrene-butadiene nibber, styrene-isoprene-butadiene rubber, isoprene-butadiene rubber, ethylene- propylene diene rubber or natural rubber.
  • the colorable rubber compositions have sufficient properties to function as a reinforcing member in an automobile tire.
  • both the transparent and colorable elastomeric compositions include at least one copolymer of a C to C isoolefin and a para-alkylstyrene, silica and a coupling agent.
  • the elastomeric compositions of the present invention are useful in a variety of applications, particularly pneumatic tire components, hoses, belts, solid tires, footwear components, rollers for graphic arts applications, vibration isolation devices, pharmaceutical devices, adhesives, sealants, protective coatings and bladders for fluid retention and curing purposes.
  • Figure 1 is a graphic illustration of the relationship between the Tan ⁇ and Temperature for the polymer product produced in Example 7.
  • an elastomeric composition is produced which exhibits transparent properties.
  • transparent as used herein is defined as transmission of light without substantial scattering such that visual identification can be made of objects behind the cured elastomeric composition. Degrees of transparency can vary from contact transparency to complete transparency.
  • the transparent elastomer compositions of the present invention do not contain carbon black.
  • the transparent feature of the composition is obtained in part by using fillers which are finer than the wavelength of visible light. Silica is preferred as the filler, however other non-black fillers such as clays, talcs and other mineral fillers may be used.
  • the remaining components of the final composition are selected on the basis that they will not interfere with the transparent nature of the elastomer.
  • the transparent elastomeric compositions of the present invention can be covulcanized with polybutadiene, polyisoprene, styrene-butadiene rubber, styrene- isoprene-butadiene rubber, isoprene-butadiene rubber, ethylene-propylene diene rubber or natural rubber.
  • they contain at least one copolymer of a C 4 to C 7 isoolefin and a para-alkylstyrene.
  • the C to C 7 isoolefin is isobutylene.
  • the para-alkylstyrene is preferably para-methylstyrene.
  • the copolymer is a terpolymer of isobutylene, para-methylstyrene and bromo para-methylstyrene.
  • the transparent elastomeric compositions of the present invention contain from 10 to 100 parts, per hundred parts rubber, of a copolymer of a C 4 to C 7 isoolefin and a para-alkylstyrene; from 10 to 100 parts of silica; and from 0 to 20 weight percent of a coupling agent, based on the weight of silica. Furthermore, the elastomeric compositions will exhibit contact transparency.
  • the transparent elastomeric compositions will also contain from 10 to 90 parts, per hundred parts rubber, of polybutadiene, polyisoprene, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, isoprene-butadiene rubber, ethylene-propylene diene rubber, or blends thereof.
  • the transparent elastomeric compositions will contain from 30 to 80 parts, per hundred parts rubber, of polybutadiene, polyisoprene, styrene- butadiene rubber, styrene-isoprene-butadiene rubber, isoprene-butadiene rubber, ethylene-propylene diene rubber, or blends thereof.
  • the copolymer used in the transparent elastomeric compositions of the present invention is preferably a terpolymer of isobutylene, para-methylstyrene and bromo para-methylstyrene.
  • this terpolymer preferably composes from 20 to 100 parts, per hundred parts rubber, of the transparent elastomeric composition. More preferably, the terpolymer composes from 30 to 80 parts, per hundred parts rubber, of the transparent elastomeric composition.
  • the silica used in the transparent elastomeric compositions of the present invention is preferably precipitated silica. Also, the precipitated silica preferably composes from 30 to 80 parts of the transparent elastomeric composition.
  • the coupling agent used in the transparent elastomeric compositions of the present invention is preferably an organosilane-coupling agent.
  • the organosilane-coupling agent composes from 2 to 15 weight percent, based on the weight of silica, of the transparent elastomeric composition. More preferably, it composes from 3 to 10 weight percent.
  • the transparent elastomers of the present invention will have utility in the areas of transparent tire sidewalls, transparent tire treads, transparent footwear, bladders, shoe soles, rollers and wiper blades.
  • an elastomer blend is produced which is colorable.
  • colorable is defined as the ability of the base elastomeric composition to be pigmented to afford a variety of colored compositions. These compositions typically do not contain carbon black.
  • the colorable rubber compositions of the present invention have sufficient properties to function as a reinforcing member in an automobile tire. Preferably, they have sufficient properties to function as an automobile tire tread.
  • the colorable rubber compositions of the present invention preferably contain at least one copolymer of a C to C 7 isoolefin and a para-alkylstyrene. More preferably, the copolymer is a terpolymer of isobutylene, para-methylstyrene and bromo para- methylstyrene.
  • the colorable rubber compositions of the present invention contain from 10 to 100 parts, per hundred parts rubber, of a copolymer of a C to C 7 isoolefin and a para-alkylstyrene; from 10 to 100 parts of silica; and from 0 to 20 weight percent of a coupling agent, based on the weight of silica.
  • the colorable rubber compositions of the present invention preferably contain from 10 to 90 parts, per hundred parts rubber, of polybutadiene, polyisoprene, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, isoprene-butadiene rubber, ethylene-propylene diene rubber, or blends thereof.
  • the colorable rubber compositions will contain from 30 to 90 parts, per hundred parts rubber, of polybutadiene, polyisoprene, styrene-butadiene nibber, styrene-isoprene-butadiene rubber, isoprene-butadiene rubber, ethylene- propylene diene rubber, or blends thereof.
  • the copolymer used in the colorable rubber compositions of the present invention is preferably a terpolymer of isobutylene, para-methylstyrene and bromo para-methylstyrene.
  • this terpolymer preferably composes from 20 to 100 parts, per hundred parts nibber, of the colorable rubber composition. More preferably, the terpolymer composes from 20 to 80 parts, per hundred parts rubber, of the colorable rubber composition.
  • the silica used in the colorable rubber compositions of the present invention is preferably precipitated silica.
  • the precipitated silica preferably composes from 30 to 80 parts of the colorable rubber composition. More preferably, it composes from 40 to 70 parts.
  • the coupling agent used in the colorable rubber compositions of the present invention is preferably an organosilane-coupling agent.
  • the organosilane-coupling agent composes from 2 to 15 weight percent, based on the weight of silica, of the colorable rubber composition. More preferably, it composes from 3 to 10 weight percent.
  • the colorable rubber compounds of the present invention are useful in making colored elastomeric products capable of meeting current performance requirements. These colorable compounds were produced by replacing carbon black filler with a non-staining mineral filler such as, but not limited to, fumed or precipitated silicas, clays, talcs, calcium carbonates, aluminum oxides, titanium oxides, silicon oxides and zinc oxides.
  • a non-staining mineral filler such as, but not limited to, fumed or precipitated silicas, clays, talcs, calcium carbonates, aluminum oxides, titanium oxides, silicon oxides and zinc oxides.
  • the mineral filler must reinforce the polymer system and not inhibit pigmentation to be effective.
  • the remaining components of the colorable compound were selected on the basis that they will not interfere with the colorable nature of the elastomer.
  • the cured, colorable compounds of the present invention still have the same dynamic and physical properties that meet the performance demands of current black-colored tire treads.
  • the transparent and colorable elastomeric compositions must be carefully selected so that they will not interfere with the transparency and/or colorability of the composition.
  • the elastomers, fillers, processing aids, antidegradants and curatives should not discolor the composition during the formation of the elastomeric composition.
  • the components should not discolor the elastomeric composition as a result of exposure to light (including UV), heat, oxygen, ozone and strain.
  • the fillers of the present invention may be any size and typically range, e.g., in the tire industry, from about 0.0001 to about 100 microns.
  • silica is meant to refer to any type or particle size silica or another silicic acid derivative, or silicic acid, processed by solution, pyrogenic or the like methods and having a surface area, including untreated, precipitated silica, crystalline silica, colloidal silica, aluminum or calcium silicates, fumed silica, and the like.
  • One or more coupling agents are preferably used in the elastomeric compositions of the present invention. More preferably, the coupling agent is a bifunctional organosilane cross-linking agent.
  • organosilane cross-linking agent is meant any silane coupled filler and/or cross linking activator and/or silane reinforcing agent known to those skilled in the art including, but not limited to, vinyl triethoxysilane, vinyl-tris-(beta-methoxyethoxy)silane, gamma- methacryloylpropyltrimethoxysilane, gamma-amino-propyl triethoxysilane (sold commercially as "Al 100" by Witco), gamma-mercaptopropyltrimethoxysilane and the like, and mixtures thereof.
  • bis-(3(triethoxysilyl)- propyl)-tetrasulfane sold commercially as "S
  • the copolymer of a C 4 to C 7 isoolefin and a para-alkylstyrene of the present invention also encompasses terpolymers of a C 4 to C isoolefin, para-alkylstyrene and halogenated para-alkylstyrene.
  • the percentages of para-alkylstyrene and halogenation can vary widely. Different applications may require dramatically different formulations.
  • the copolymer of the present invention will have from 2 wt. % to 20 wt. % para-alkylstyrene (preferably para-methylstyrene).
  • the copolymer of the present invention will have from 0.20 mol % to 2.0 mol % of a halogenated compound, such as bromomethylstyrene.
  • para-alkylstyrene (preferably para-methylstyrene) comprises from 5 wt. % to 10 wt. % of the copolymer. More preferably, it is less than 10 wt. % of the copolymer.
  • a halogenated compound, such as bromomethylstyrene comprises from 0.40 mol % to 3.0 mol % of the copolymer. More preferably, it comprises from 0.50 mol % to 1.25 mol % of the copolymer. Most preferably, it is about 0.75 mol % of the copolymer.
  • compositions produced in accordance with the present invention may also contain other components and additives customarily used in rubber mixes, such as effective amounts of nondiscolored and nondiscoloring processing aids, pigments, accelerators, cross-linking and curing materials, antioxidants, antiozonants, fillers and naphthenic, aromatic or paraffinic extender oils if the presence of an extension oil is desired.
  • Processing aids include, but are not limited to, plasticizers, tackifiers, extenders, chemical conditioners, homogenizing agents and peptizers such as mercaptans, petroleum and vulcanized vegetable oils, waxes, resins, rosins, and the like.
  • Accelerators include amines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates, and the like.
  • Cross-linking and curing agents include sulfur, zinc oxide, and fatty acids. Peroxide cure systems may also be used.
  • Fillers include mineral fillers such as silica and clay.
  • the present invention provides improved elastomeric compositions comprising a copolymer of a C 4 to C 7 isoolefin and a para-alkylstyrene, silica and, optionally, one or more coupling agents. These compositions exhibit improved properties including improved abrasion resistance, reduced cut growth, improved adhesion, reduced heat build-up, and retention of mechanical properties during severe heat build-up conditions such as those experienced in "run-flat" tires and engine mounts for transportation vehicles.
  • the substantially isoolefin (isobutylene) backbone elastomer is a key element in that it imparts a self-limiting heat build-up.
  • these elastomers exhibit high damping behavior which dissipates mechanical energy in the form of heat. However, as the elastomer heats up, the damping behavior diminishes and the behavior of the elastomer in more elastic and less dissipative.
  • polymer blends e.g., those used to produce tires
  • polymer blends may be crosslinked by adding curative molecules, for example sulfur, metal oxides (i.e., zinc oxide), organometallic compounds, radical initiators, etc. followed by heating.
  • This method may be accelerated and is often used for the vulcanization of elastomer blends.
  • the mechanism for accelerated vulcanization of natural rubber involves complex interactions between the curative, accelerator, activators and polymers. Ideally, all of the available curative is consumed in the formation of effective crosslinks which join together two polymer chains and enhance the overall strength of the polymer matrix.
  • curatives include, but are not limited to, the following: zinc oxide, stearic acid, tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), benzothiazyl disulfide (MBTS), hexamethylene-l,6-bisthiosulfate disodium salt dihydrate (sold commercially as DURALENK HTS by Flexsys), 2-(morpholinothio) benzothiazole (MBS or MOR), blends of 90% MOR and 10% MBTS (MOR 90), and N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide (OTOS) zinc 2-ethyl hexanoate (ZEH)
  • TMTD tetramethylthiuram disulfide
  • DTDM 4,4'-dithiodimorpholine
  • TBTD te
  • the materials are mixed by conventional means known to those skilled in the art, in a single step or in stages
  • the elastomers of this invention can be processed in one step
  • the silica and silane are added in a different stage from zinc oxide and other cure activators and accelerators
  • antioxidants, antiozonants and processing materials are added in a stage after silica and silane have been processed with the rubber, and zinc oxide is added at a final stage to maximize compound modulus
  • a two to three (or more) stage processing sequence is preferred Additional stages may involve incremental additions of filler and processing oils
  • the elastomeric compositions of the present invention are not only transparent, but can be covulcanized with other rubbers This results in a transparent elastomer that can be used in wide variety of applications outside of the uses for known transparent elastomers
  • the transparent elastomeric compositions of the present invention can be used in tires
  • the colorable elastomeric compositions of the present invention exhibit improved hysteretic properties, traction, heat stability and retention of properties upon aging to known colorable elastomers This results in colorable rubber compositions which have sufficient properties to function as a reinforcing member in an automobile tire
  • the colorable rubber will allow a manufacturer to produce a tire with improved product appearance
  • the elastomeric compositions of the present invention are useful in a variety of applications, particularly pneumatic tire components, hoses, belts, solid tires, footwear components, rollers for graphic arts applications, vibration isolation devices, pharmaceutical devices, adhesives, sealants, protective coatings and bladders for fluid retention and curing purposes.
  • Test compositions were compounded to blend the master batch components and the cure additives listed in Table 2.
  • FLEXON 785 is a naphthenic petroleum oil.
  • DIAK #1 is hexamethylene diamine carbonate, available from Du Pont/Dow elastomers.
  • DPG is diphenylguanidine.
  • test compositions (A through F) were tested for cure characteristics, hardness and tensile strength. The results are presented in Table 3.
  • Example 2 A Minolta CR-100 ChromaMeter was used to quantitatively determine the lightness (L*), red-green (a*) and yellow-blue (b*) colors of cured compounds in order to maximize light through-put (a measure of transparency) and to minimize or adjust the color.
  • the ability to read print through these cured rubber compounds was also used as a subjective evaluation of the contact transparency of the ingredients in the formulation.
  • Statistically designed experiments varying ingredients, and statistical analysis of variance (ANOVA) for effects on compound cure, physical and color properties were made.
  • EXXPROTM elastomers with statistically varying para-methylstyrene and bromomethylstyrene levels were evaluated in a simple compound prepared only with precipitated silica and a zinc oxide/zinc stearate cure system. It was established that low levels of either bromine and/or para- methylstyrene provided the highest L* values with low, but not negative, a* and b* values, see Table 4.
  • EXXPROTM 89-1 (5 wt-% pMS, 0.75 mol-% Br) afforded the highest L* and lowest a* and b* values.
  • curative types thought useful in co-curing with the other sulfur- vulcanized tire compounds were screened.
  • Acceptable curatives were zinc oxide/stearic acid; zinc oxide/zinc stearate; Hexamethylene- l,6-bis(thiosulphate) disodium salt dihydrate (sold commercially as DURALINK HTS by Flexsys)/zinc stearate; DURALINK HTS/zinc oxide; and l,3-Bis(citraconimidomethyl)benzene (sold commercially as PERKALINK 900 by Flexsys)/zinc stearate, since their use afforded transparent compounds from nearly colorless to a yellow or beige color.
  • CBS N-cyclohexyl-2-benzothiazole sulfenamide
  • amylphenyl disulfide polymer (18.5-21% sulfur) (sold commercially as VTJLTAC 5 by Elf Atochem North America) afforded a grey compound
  • Precipitated silicas made via an aqueous acidification process were screened using EXXPROTM 89-1 as the elastomer and Duralink HTS/ zinc stearate as the curative system. It was observed that for precipitated silicas having approximately the same CTAB surface area (approximately 170 m 2 /g), use of a precipitated silica having a higher salt content afforded a brown-colored transparent compound (Zeosil 1 165MP from Rhone Poulenc) compared to lower salt-content precipitated silicas which afforded yellow-colored transparent compounds.
  • Example 5 Transparent cured EXXPROTM 1 compounds were prepared in blends with cis-polyisoprene and/or cis-polybutadiene using precipitated and fumed silicas as the fillers, and a sulfur curing system. All cured compounds were contact transparent, but had a yellow to brown color depending upon the specific ingredients, and afforded compounds with physical properties appropriate for use in a variety of bber applications. Examples are shown in Table 5. Table 5. Formulations and Properties of Transparent Rubber Compounds
  • Example 6 A formulation for a colorable tire tread was prepared, see Table 6. This formulation differs from a standard tire tread formulation in several ways. For example, EXXPROTM polymers are used instead of an equal weight of solution- polymerized SBR to improve cured compound dynamic and physical properties. Also, Si69 is used as the silane-coupling agent instead of the more common X50S (which is 50%) by weight Si69 carried on N330 carbon black). In addition, no antiozonant is used since this can also stain or discolor the tread composition. Compound colorability can be further improved by using titanium dioxide as a non- reinforcing, but whitening pigment.
  • EXXPROTM polymers are used instead of an equal weight of solution- polymerized SBR to improve cured compound dynamic and physical properties.
  • Si69 is used as the silane-coupling agent instead of the more common X50S (which is 50%) by weight Si69 carried on N330 carbon black).
  • no antiozonant is used since this can also stain or discolor the tread composition. Compound color
  • Example 7 The viscoelastic nature of EXXPROTM elastomers increases the loss modulus (G") or tangent delta values of the cured compound measured at 0°C, see Figure 1.
  • This dynamic value is a laboratory test useful in predicting the wet traction performance of tread compounds on tires. A higher value is desirable.
  • the tangent delta value measured at 60°C in lab instruments is reduced when using EXXPROTM elastomers (see Figure 1) indicating a lower heat build-up value. This is predictive of tire rolling resistance. A lower value is desirable.
  • the complex modulus value (G*) measured at 60°C is used as a lab predictor of the dry handling, or cornering, characteristics of the tread compound on the tire.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

L'invention concerne des compositions élastomères transparentes et des compositions élastomères colorables. Les compositions transparentes peuvent être covulcanisées avec des caoutchoucs tels que le polybutadiène, le polyisoprène, le butadiène-styrène, le styrène-isoprène-butadiène, l'isoprène-butadiène, l'éthylène-propylène-diène ou un caoutchouc naturel. Les compositions colorables ont des propriétés leur permettant de servir d'élément de renforcement dans un pneu d'automobile. De préférence, les compositions élastomères transparentes et les compositions élastomères colorables renferment au moins un copolymère constitué d'une iso-oléfine C4-C7 et d'un para-alkylstyrène, de la silice et un agent de couplage.
PCT/US1998/026716 1997-12-15 1998-12-15 Compositions elastomeres transparentes et colorables WO1999031178A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP2000539089A JP2002508425A (ja) 1997-12-15 1998-12-15 透明な及び着色可能なエラストマー性組成物
DE69817398T DE69817398T2 (de) 1997-12-15 1998-12-15 Transparente und färbbare elastomerzusammensetzung
AT98963235T ATE247691T1 (de) 1997-12-15 1998-12-15 Transparente und färbbare elastomerzusammensetzung
EP98963235A EP1040163B1 (fr) 1997-12-15 1998-12-15 Compositions elastomeres transparentes et colorables
BR9814192-9A BR9814192A (pt) 1997-12-15 1998-12-15 Composições elastoméricas transparentes e tingìveis
CA002306270A CA2306270A1 (fr) 1997-12-15 1998-12-15 Compositions elastomeres transparentes et colorables
KR1020007005237A KR20010032104A (ko) 1997-12-15 1998-12-15 투명하고 착색가능한 탄성중합체성 조성물

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US6959997P 1997-12-15 1997-12-15
US60/069,599 1997-12-15

Publications (1)

Publication Number Publication Date
WO1999031178A1 true WO1999031178A1 (fr) 1999-06-24

Family

ID=22090034

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/026716 WO1999031178A1 (fr) 1997-12-15 1998-12-15 Compositions elastomeres transparentes et colorables

Country Status (12)

Country Link
US (1) US6624235B1 (fr)
EP (1) EP1040163B1 (fr)
JP (1) JP2002508425A (fr)
KR (1) KR20010032104A (fr)
CN (1) CN1278842A (fr)
AT (1) ATE247691T1 (fr)
BR (1) BR9814192A (fr)
CA (1) CA2306270A1 (fr)
DE (1) DE69817398T2 (fr)
ES (1) ES2205592T3 (fr)
PL (1) PL340301A1 (fr)
WO (1) WO1999031178A1 (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001096462A3 (fr) * 2000-06-13 2002-04-11 Exxonmobil Chem Patents Inc Compositions d'elastomeres transparentes et colorables
WO2001096463A3 (fr) * 2000-06-13 2002-05-23 Exxonmobil Chem Patents Inc Procede de preparation de compositions elastomeres contenant une charge de silice
EP1228898A1 (fr) * 2001-02-01 2002-08-07 The Goodyear Tire & Rubber Company Bande de roulement avec couche de recouvrement coextrudée et non-noire
US6515063B2 (en) * 2001-02-01 2003-02-04 The Goodyear Tire & Rubber Company Tire having colored tread
US6525128B2 (en) * 2001-02-01 2003-02-25 The Goodyear Tire & Rubber Company Composition of organophosphite, isobutylene copolymer and silica and tire thereof
US6561244B2 (en) 2001-02-01 2003-05-13 The Goodyear Tire & Rubber Company Tire having tread with colored groove configuration
US6624235B1 (en) 1997-12-15 2003-09-23 Exxonmobil Chemical Patents Inc. Transparent and colorable elastomeric compositions
EP1228902A3 (fr) * 2001-02-01 2003-10-22 The Goodyear Tire & Rubber Company Pneu ayant une bande de roulement dont le flanc est colorés non noir, combinée avec des rainures colorées non noires
US6710116B1 (en) 2000-10-18 2004-03-23 Exxonmobil Chemical Patents Inc. Abrasion resistant transparent and colorable elastomeric compositions
WO2004005395A3 (fr) * 2002-07-09 2004-08-05 Gen Electric Mélanges de silice-caoutchouc à dureté améliorée
EP1404754A4 (fr) * 2001-06-07 2004-09-08 Exxonmobil Chem Patents Inc Copolymeres a base d'isobutylene halogene a viscosite renforcee et composition thermoplastique constituee de ces copolymeres
US6939921B2 (en) 2001-10-16 2005-09-06 Exxonmobil Chemical Patents Inc. Colorable elastomeric composition
EP1241213A3 (fr) * 2001-03-15 2005-11-30 The Goodyear Tire & Rubber Company Pneu avec bande de roulement à base de composition de caoutchouc contenant 1,3-bis-(citraconimidomethyl) benzène ou pentaérythritol triacrylate
EP1498453A4 (fr) * 2002-04-25 2006-03-29 Asahi Kasei Chemicals Corp Composition de caoutchouc et procede de production
US7282269B2 (en) 2001-06-04 2007-10-16 Exxonmobil Chemical Patents Inc. Cured rubber components for use with pharmaceutical devices
US7338688B2 (en) 2001-06-04 2008-03-04 Exxonmobil Chemical Patents Inc. Protective pipe and tank linings
EP1864688A3 (fr) * 2006-06-08 2008-03-12 Belgian Diagnostic Company S.A. Bouchon pour l'obturation d'une embase creuse de cathéter
RU2319716C2 (ru) * 2001-12-10 2008-03-20 Эксонмобил Кемикэл Пейтентс Инк. Эластомерные композиции
US7425591B2 (en) 2001-10-16 2008-09-16 Exxonmobil Chemical Patents Inc Elastomeric composition
EP1803587A3 (fr) * 2005-12-28 2008-12-24 The Goodyear Tire & Rubber Company Bande de roulement ayant des particules discrètes, dont la couleur est différente de celle de la bande de roulement
WO2015130322A1 (fr) * 2014-02-26 2015-09-03 Pacesetter Graphic Service Corporation Rouleau d'impression flexible à durabilité élevée
EP2812387B1 (fr) 2012-02-06 2016-05-04 Wacker Chemie AG Matières à base de polymères à terminaison organyloxysilane

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7179857B2 (en) * 1998-08-20 2007-02-20 Rhodia Chimie Use of titanium dioxide as anti-UV agent in a rubber composition
WO2006071312A2 (fr) * 2004-12-29 2006-07-06 Exxonmobil Chemical Patents Inc. Melanges elastomeres selectionnes et leur utilisation dans des articles
KR100454284B1 (ko) * 2001-12-27 2004-10-26 한국신발피혁연구소 고신장성 고무 조성물의 제조방법
US7201944B2 (en) * 2002-12-18 2007-04-10 Bridgestone Firestone North American Tire, Llc Rubber compositions and articles thereof having improved metal adhesion and metal adhesion retention with bright steel
JP2005126471A (ja) * 2003-10-21 2005-05-19 Sumitomo Rubber Ind Ltd サイドウォール用ゴム組成物およびそれを用いた空気入りタイヤ
CN1298778C (zh) * 2003-12-19 2007-02-07 清华大学 羧基功能型高分子/SiO2复合纳米粒子及其制备方法
KR100738670B1 (ko) * 2006-03-27 2007-07-11 금호타이어 주식회사 타이어 트레드 고무조성물
US7625965B2 (en) * 2007-02-08 2009-12-01 Momentive Performance Materials Inc. Rubber composition, process of preparing same and articles made therefrom
KR100871279B1 (ko) 2007-09-18 2008-11-28 금호타이어 주식회사 타이어 트레드용 고무조성물
JP5510821B2 (ja) * 2010-06-02 2014-06-04 住友ゴム工業株式会社 タイヤ用加硫ゴム組成物およびそれを用いた空気入りタイヤ
IT1403426B1 (it) * 2010-12-23 2013-10-17 Bridgestone Corp Mescola per battistrada comprendente trialcossimercaptoalchil-silani
CN106188655A (zh) * 2015-05-06 2016-12-07 中山市奔点五金机械有限公司 一种弹力轮及其制备方法
US11254763B2 (en) 2019-02-12 2022-02-22 Exxonmobil Chemical Patents Inc. Transition metal bis(phenolate) complexes and their use as catalysts for olefin polymerization

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986002088A1 (fr) * 1984-09-28 1986-04-10 Battelle Development Corporation Elastomeres optiquement transparents
US5013793A (en) * 1990-07-26 1991-05-07 Exxon Chemical Patents Inc. Dynamically cured thermoplastic olefin polymers and process for producing the same
WO1992016587A1 (fr) * 1991-03-21 1992-10-01 Exxon Chemical Patents Inc Composition pour elements de cuisson en moule
DE4308311A1 (de) * 1993-03-16 1994-09-22 Degussa Verwendung gefällter Kieselsäuren mit hoher spez. Oberfläche zur Verbesserung der Transparenz und Helligkeitseigenschaften vulkanisierbarer heller Kautschukmischungen
EP0682071A1 (fr) * 1994-05-05 1995-11-15 The Goodyear Tire & Rubber Company Bande de roulement renforcée quantitativement par de la silice

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3824160A (en) 1972-05-26 1974-07-16 Allied Chem Manufacture of copper dichromate and related materials
US4074035A (en) * 1975-04-22 1978-02-14 Exxon Research & Engineering Co. Halomethylated aromatic interpolymers
US5567775A (en) * 1989-11-27 1996-10-22 Exxon Chemical Patents Inc. Craft curing of modified isomonoolefin/para-alkylstyrene copolymers
US5063268A (en) 1990-06-08 1991-11-05 Exxon Chemical Patents Inc. Composition for tire treads (E-235)
EP0533746A1 (fr) 1990-06-15 1993-03-31 Exxon Chemical Patents Inc. Composition pour dispositifs dynamiques
US5333662A (en) 1990-07-18 1994-08-02 Exxon Chemical Patents Inc. Tire innerliner composition
US5532312A (en) 1990-08-15 1996-07-02 Exxon Chemical Patents, Inc. Tire sidewall composition
DE69123849T2 (de) 1990-08-15 1997-04-10 Exxon Chemical Patents Inc Mischung für reifenseitenwand
FR2673187B1 (fr) 1991-02-25 1994-07-01 Michelin & Cie Composition de caoutchouc et enveloppes de pneumatiques a base de ladite composition.
US5162409B1 (en) 1991-08-02 1997-08-26 Pirelli Armstrong Tire Corp Tire tread rubber composition
US5376438A (en) 1993-02-08 1994-12-27 Exxon Chemical Patents Inc. Multilayer tire sidewall
CN1278842A (zh) 1997-12-15 2001-01-03 埃克森化学专利公司 透明和可着色的弹性体组合物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986002088A1 (fr) * 1984-09-28 1986-04-10 Battelle Development Corporation Elastomeres optiquement transparents
US5013793A (en) * 1990-07-26 1991-05-07 Exxon Chemical Patents Inc. Dynamically cured thermoplastic olefin polymers and process for producing the same
WO1992016587A1 (fr) * 1991-03-21 1992-10-01 Exxon Chemical Patents Inc Composition pour elements de cuisson en moule
DE4308311A1 (de) * 1993-03-16 1994-09-22 Degussa Verwendung gefällter Kieselsäuren mit hoher spez. Oberfläche zur Verbesserung der Transparenz und Helligkeitseigenschaften vulkanisierbarer heller Kautschukmischungen
EP0682071A1 (fr) * 1994-05-05 1995-11-15 The Goodyear Tire & Rubber Company Bande de roulement renforcée quantitativement par de la silice

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6624235B1 (en) 1997-12-15 2003-09-23 Exxonmobil Chemical Patents Inc. Transparent and colorable elastomeric compositions
US6624220B1 (en) 1997-12-15 2003-09-23 Exxonmobil Chemical Patents Inc. Transparent and colorable elastomeric compositions
WO2001096463A3 (fr) * 2000-06-13 2002-05-23 Exxonmobil Chem Patents Inc Procede de preparation de compositions elastomeres contenant une charge de silice
WO2001096462A3 (fr) * 2000-06-13 2002-04-11 Exxonmobil Chem Patents Inc Compositions d'elastomeres transparentes et colorables
EP1345990A4 (fr) * 2000-10-18 2004-04-21 Exxonmobil Chem Patents Inc Composition lastom re colorable
US6710116B1 (en) 2000-10-18 2004-03-23 Exxonmobil Chemical Patents Inc. Abrasion resistant transparent and colorable elastomeric compositions
US6515063B2 (en) * 2001-02-01 2003-02-04 The Goodyear Tire & Rubber Company Tire having colored tread
EP1331107A1 (fr) * 2001-02-01 2003-07-30 The Goodyear Tire & Rubber Company Bande de roulement avec des rainures colorées
US6583210B2 (en) 2001-02-01 2003-06-24 The Goodyear Tire & Rubber Company Tire having tread with co-extruded non-black colored overlay
US6561244B2 (en) 2001-02-01 2003-05-13 The Goodyear Tire & Rubber Company Tire having tread with colored groove configuration
EP1228902A3 (fr) * 2001-02-01 2003-10-22 The Goodyear Tire & Rubber Company Pneu ayant une bande de roulement dont le flanc est colorés non noir, combinée avec des rainures colorées non noires
US6525128B2 (en) * 2001-02-01 2003-02-25 The Goodyear Tire & Rubber Company Composition of organophosphite, isobutylene copolymer and silica and tire thereof
EP1228898A1 (fr) * 2001-02-01 2002-08-07 The Goodyear Tire & Rubber Company Bande de roulement avec couche de recouvrement coextrudée et non-noire
EP1241213A3 (fr) * 2001-03-15 2005-11-30 The Goodyear Tire & Rubber Company Pneu avec bande de roulement à base de composition de caoutchouc contenant 1,3-bis-(citraconimidomethyl) benzène ou pentaérythritol triacrylate
US7338688B2 (en) 2001-06-04 2008-03-04 Exxonmobil Chemical Patents Inc. Protective pipe and tank linings
US7282269B2 (en) 2001-06-04 2007-10-16 Exxonmobil Chemical Patents Inc. Cured rubber components for use with pharmaceutical devices
US7226962B2 (en) 2001-06-07 2007-06-05 Exxonmobil Chemical Patents Inc. Halogenated isobutylene-based copolymers having enhanced viscosity and thermoplastic compositions thereof
EP1404754A4 (fr) * 2001-06-07 2004-09-08 Exxonmobil Chem Patents Inc Copolymeres a base d'isobutylene halogene a viscosite renforcee et composition thermoplastique constituee de ces copolymeres
US7425591B2 (en) 2001-10-16 2008-09-16 Exxonmobil Chemical Patents Inc Elastomeric composition
US6939921B2 (en) 2001-10-16 2005-09-06 Exxonmobil Chemical Patents Inc. Colorable elastomeric composition
US7451529B2 (en) 2001-10-16 2008-11-18 Exxonmobil Chemical Patents Inc. Colorable elastomeric composition
RU2319716C2 (ru) * 2001-12-10 2008-03-20 Эксонмобил Кемикэл Пейтентс Инк. Эластомерные композиции
US7132471B2 (en) 2002-04-25 2006-11-07 Asahi Kasei Chemicals Corporation Rubber composition and process for production thereof
EP1498453A4 (fr) * 2002-04-25 2006-03-29 Asahi Kasei Chemicals Corp Composition de caoutchouc et procede de production
WO2004005395A3 (fr) * 2002-07-09 2004-08-05 Gen Electric Mélanges de silice-caoutchouc à dureté améliorée
KR101053009B1 (ko) * 2002-07-09 2011-07-29 제너럴 일렉트릭 캄파니 경도가 개선된 실리카-고무 혼합물
US7432321B2 (en) 2002-07-09 2008-10-07 Momentive Performance Materials Inc. Silica-rubber mixtures having improved hardness
EP1803587A3 (fr) * 2005-12-28 2008-12-24 The Goodyear Tire & Rubber Company Bande de roulement ayant des particules discrètes, dont la couleur est différente de celle de la bande de roulement
US7530378B2 (en) 2005-12-28 2009-05-12 The Goodyear Tire & Rubber Company Speckled tire treads
EP1864688A3 (fr) * 2006-06-08 2008-03-12 Belgian Diagnostic Company S.A. Bouchon pour l'obturation d'une embase creuse de cathéter
EP2812387B1 (fr) 2012-02-06 2016-05-04 Wacker Chemie AG Matières à base de polymères à terminaison organyloxysilane
US10077386B2 (en) 2012-02-06 2018-09-18 Wacker Chemie Ag Compositions on the basis of organyloxysilane-terminated polymers
EP2812387B2 (fr) † 2012-02-06 2019-03-06 Wacker Chemie AG Matières à base de polymères à terminaison organyloxysilane
WO2015130322A1 (fr) * 2014-02-26 2015-09-03 Pacesetter Graphic Service Corporation Rouleau d'impression flexible à durabilité élevée
US9579882B2 (en) 2014-02-26 2017-02-28 Pacesetter Graphic Service Corporation High durability pliable print roller

Also Published As

Publication number Publication date
JP2002508425A (ja) 2002-03-19
DE69817398T2 (de) 2004-06-09
CN1278842A (zh) 2001-01-03
CA2306270A1 (fr) 1999-06-24
KR20010032104A (ko) 2001-04-16
DE69817398D1 (de) 2003-09-25
ES2205592T3 (es) 2004-05-01
EP1040163B1 (fr) 2003-08-20
PL340301A1 (en) 2001-01-29
EP1040163A1 (fr) 2000-10-04
ATE247691T1 (de) 2003-09-15
BR9814192A (pt) 2000-09-26
US6624235B1 (en) 2003-09-23

Similar Documents

Publication Publication Date Title
EP1040163B1 (fr) Compositions elastomeres transparentes et colorables
US6710116B1 (en) Abrasion resistant transparent and colorable elastomeric compositions
US6624220B1 (en) Transparent and colorable elastomeric compositions
US6939921B2 (en) Colorable elastomeric composition
US7385008B2 (en) Abrasion resistant elastomeric compositions
WO2001096463A2 (fr) Procede de preparation de compositions elastomeres contenant une charge de silice
US20040063859A1 (en) High traction and wear resistant elastomeric compositions
US20040014869A1 (en) Method for preparing silica filled elastomeric compositions

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 98811139.X

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): BR CA CN CZ HU JP KR MX PL

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
ENP Entry into the national phase

Ref document number: 2306270

Country of ref document: CA

Ref document number: 2306270

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PV2000-1766

Country of ref document: CZ

WWE Wipo information: entry into national phase

Ref document number: 1020007005237

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 2000 539089

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1998963235

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 200000666

Country of ref document: EA

WWP Wipo information: published in national office

Ref document number: 1998963235

Country of ref document: EP

WWR Wipo information: refused in national office

Ref document number: PV2000-1766

Country of ref document: CZ

WWP Wipo information: published in national office

Ref document number: 1020007005237

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1998963235

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1020007005237

Country of ref document: KR

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载